Halogenated epoxides

ABSTRACT

Trihaloneopentyl alcohol is reacted with epihalohydrin and then with base to give an adduct of the formula WHERE EACH X and X&#39;&#39; is independently Br or Cl and n is an integer of 0 to about 10. Such compounds are useful as plasticizers for polyvinyl chloride, as fire retardants for polyesters, and as intermediates.

United States Patent Gibbons July 4, 1972 [54] HALOGENATED EPOXIDESPrimary Examiner-Norma S. Milestone Attorney-Griswold & Burdick, HerbertD. Knudsen and C. E. Rehberg [57] ABSTRACT Trihaloneopentyl alcohol isreacted with epihalohydrin and then with base to give an adduct of theformula where each X and X is independently Br or Cl and n is an integerof 0 to about 10. Such compounds are useful as plasticizers forpolyvinyl chloride, as fire retardants for polyesters, and asintermediates.

7 Claims, No Drawings HALOGENATED EPOXIDES BACKGROUND OF THE INVENTIONHalogenated epoxides are well known in the an, especially those epoxidesobtained from epichlorohydrin. The compounds of the present invention,however, are not known and their unusual properties could not have beenpredicted from the art.

Plasticizers for polyvinyl chloride have been continuously sought,especially those plasticizers which lend fire retardancy to polyvinylchloride rather than deleteriously affect the fire retardancy of theresultant product. This search along with a search for a suitable fireretardant for polyesters has spurred research to find suitable compoundswhich have desirable propertics to fulfill either of these needs.

Polyepihalohydrins have been employed as additives in acrylonitrilepolymer along with other substances such as calcium phosphates andantimony oxide, see Lowes in US. Pat. Nos. 3,271,343 and 3,271,344. Suchcombinations gave films that were fire retardant.

SUMMARY OF THE INVENTION According to the present invention, newhalogenated epoxides of the general formula where each X and x' isindependently Br or Cl and n is an integer of to about 10 have beendiscovered. Such compounds are good plasticizers for polyvinyl chlorideand are suitable fire retardants for polyesters.

The compounds contemplated by the invention are any of those which fitthe general formula above. Preferred compounds of the invention arethose wherein each X is Br and those compounds wherein each X is Cl.Especially preferred are those compounds wherein each X is Br and each Xis Cl and those compounds wherein n is an integer of 0 to 5. Referringto specific compounds, those of special interest in the presentinvention have an n of 0 and an n of 1 respectively.

The compounds of the invention are prepared by reacting the appropriatebromo, chloro or bromochloroneopentyl alcohol with epichlorohydrin,epibromohydrin or mixtures thereof in the presence of a Lewis Acidcatalyst as the first step. When this reaction is complete, the productis reacted in a second step with caustic or other suitable base toproduce the terminal epoxide. Both reactions are well known and areconducted in the ordinary manner as exemplified in the SpecificEmbodiments.

The products of the invention are colorless high boiling liquids.Generally rather than obtaining one specific compound in the reaction, amixture of compounds varying in the value of n is obtained. The adductsof the present invention are freely soluble in many organic solventssuch as acetone, methylene chloride, ethylene dichloride, chloroform,carbon tetrachloride, benzene, methanol and toluene.

The halogenated epoxides of the invention, especially those where n isless than 5, are useful plasticizers for polyvinyl chloride to give afire retardant product. They are also useful and compatible fireretardants for polyesters. These compounds are also especially usefulintermediates for preparing ethers of compounds containing an activehydrogen such as polyglycols, and they may be hydrolyzed to givehalogenated glycols.

SPECIFIC EMBODIMENTS Example 1 To a reactor was charged 1,624 g. (5moles) of tribromoneopentyl alcohol, 1,500 ml. of ethylene dichlorideand 7.5 ml. of anhydrous stannic chloride. The reactor and contents wereheated to C. with stirring. 482 G. (5.2 m.) of epichlorohydrin was addeddropwise with stirring over a period of 1 hour using the reactionexotherm to maintain the temperature at 82 to 85 C. At the terminationof the addition of epichlorohydrin, the solution was stirred at 82 C.for 20 minutes. This solution was cooled to 70 C. and then treated with10 moles of sodium hydroxide dissolved in 1,200 ml. of water. The 2phase system was stirred vigorously at 75 C. for 40 hours. The organicphase was separated, washed with water until neutral and dried overmagnesium sulfate. The product was stripped of solvent and by-productsby vacuum distillation. The crude product was a pale yellow liquidweighing 1,240 g. The mixture was analyzed as described by lay, inAnalytical Chemistry 36, 667 (1964) to have an epoxy equivalent weightof 467 and by neutron activation analysis the product was analyzed tocontain 53.6 percent by weight Br and 6.1 percent by weight C1. Themixture in a differential thermal analysis showed exothermicdecomposition at 330 to 345 C. in thermal gravimetric analysis where thesample is gradually heated, the mixture lost weight from 150 to b 325C., with 50 percent weight loss at 250 C. Example 2 A mixture of theproduct of Example 1 containing approximately equal weight percentagesof 0 mormocnzoomonoomon H2 "CH-2C1 was blended with polyvinyl chloridesold under the trade designation PVC-2103 at a level of parts perhundred of resin. The blending was done in a Brabender mixer at C. for 5minutes at a speed of 60 rpm. The material was then molded at atemperature of 150 C. and a pressure of 20,000 psi. for 4 minutes. Thefinal product was transparent and had a flexibility roughly equivalentto that obtained by plasticizing the same resin with 60 parts perhundred of dioctyl phthalate in the same manner. The finished productcontaining the halogenated epoxide exhibited a high degree of flameretardancy and was self-extinguishing when ignited with a match or aBunsen burner flame. A sample of the product had a limiting oxygen index(101) as described in Combustion and Flame, I0, 135 1966) of 0.400 ascompared to an LOI of 0.225 for the product plasticized with a dioctylphthalate. Example 3 In the same manner as described by Example 2, aformulation containing 1 part by weight of the halogenated epoxideplasticizer of Example 1 and 1 part by weight of dioctyl phthalate wasblended and molded with polyvinyl chloride as shown in Example 2 at aconcentration of 60 parts per hundred to give a transparent material ofslightly lower flexibility than the resin plasticized only with thedioctyl phthalate at the same level. This material was alsoself-extinguishing and had an LOI of 0.280. Example 4 A polyester resinwas prepared by reacting g. of maleic anhydride, 405 g. of phthalicanhydride, 320 g. of propylene glycol and 680 g. of the mixture ofglycidyl ethers of tribromoneopentyl alcohol prepared in Example 1. Thecom ponents described above were mixed and reacted at a temperature of190 C. for 1 1 hours at atmospheric pressure. The product was dilutedwith 30 percent by weight of styrene monomer and cooked in the presenceof 1 percent of benzoyl peroxide at a temperature of F. to give a clearresin containing 15 percent by weight bromine. The polyester resin hadan LC] of 0.247 and had physical properties similar to a polyesterwithout the halogenated epoxide. Example 5 In the same manner as shownin Example 1, two molar equivalents of epichlorohydrin was reacted withtribromoneopentyl alcohol to give a mixture of compounds of the generalformula where each X was Br, each X was Cl and n had an average value ofabout 1.2. This compound was tested as shown in Example 2 and found tobe a suitable plasticizer for polyvinyl chloride.

Example 6 In the same manner as shown in Example 5, five molarequivalents of epichlorohydrin was reacted with tribromoneopentylalcohol to give a product where the average value of n was about 4. Thismixture was tested as a plasticizer for polyvinyl chloride and found togive a flexible but stiffer product than that of Example 5.

In the same manner as described by Example 1 other compounds of thegeneral formula are prepared by reacting tribromoneopentyl alcohol,trichloroneopentyl alcohol, or chlorobromoneopentyl alcohol withepichlorohydrin, epibromohydrin or mixture thereof in the presence of aLewis Acid catalyst. Representative examples of such compounds include:

which is prepared by reacting trichloroneopentyl alcohol with about 1 1moles of epichlorohydrin in the presence of stannic chloride and thenreacting one mole of aqueous NaOH per mole of hydroxyl in the resultantproduct.

Other representative compounds include:

O CHzCH-O-CHzHE Hz CHzCl These compounds are suitable plasticizers, fireretardants and intermediates as described above.

I claim:

1. A compound of the formula

2. The compound of claim 1 wherein each X is Br.
 3. The compound ofclaim 1 wherein each X'' is Cl.
 4. The compound of claim 1 wherein eachX is Br and each X'' is Cl.
 5. The compound of claim 1 wherein n is aninteger of 0 to
 5. 6. The compound of claim 1 wherein n is
 0. 7. Thecompound of claim 1 wherein n is 1.